Explosive and method of producing the same and its ingredients.



UNITED STATES PATENT OFFICE.

HAROLD HIBBERT, OF WILMINGTON, DELAWARE, ASSIO'NOR ,TO E. I. DU PONT DE NEMOURS POWDER COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF NEW JERSEY.

EXPLOSIVE AND METHOD OF PRODUCING THE SAME AND ITS INGREDIENTS.

No Drawing.

To all whom 'it may concern:

Be it known. that I, HAROLD HIBBERT, a

' subject of the King of Great Britain, residing at Wilmington, county of Newcastle, and State. of Delaware, have invented a new and useful Improvement in Explosives and Methods of Producing the Same and Its Ingredients, of which the following is a full, clear, and exact description.

When glycerin is treated with the mixed acids, nitric acid and sulfuric acid, for the production of glycerin trinitrate, glycerin trinitrate is produced, the formula of which is:

cnmo,

cauo, demo,

This glycerin trinitrate has certain defects, among which it may be stated that the glycerin which is its base is expensive, and the temperature of explosion of the explosive mixture of the glycerin trinit-rate is very high, which makesit in many cases not and heat.

a good ingredient for smokeless powder.

I have discovered that if nitrated butylene glycol be formed, a product is obtainedwhose temperature of explosive ignition is lower than that of glycerin trinitrate, which enables it to be freely used as an ingredient of smokeless powder, safety explosives and dynamite. Further, I have discovered that such compound may be combined with nitrate derivatives, such, for instance, as nitrated cellulose or nitrated starch, to form a colloid of such mixture. It alsomay be mixed with glycerintrinitrate, and the resulting mixture has a lower freezing point and is more stable than glycerin trinitrate.

While butylene glycol isknown and is described in text books, I believe myself to be the first to have discovered nitrated butylene glycol and its value for the purposes named. Further, the method of maki butylene glycol, as set out in the text books,

is so complicated as to render it very 'expensive and difiicult to carry out. My discovery, therefore, includes a simple method for directly producing this butylene glycol as well as the nitrated butylene glycol.

Specification of Letters Patent.

Patented Nov. '14, 1911."

Application filed January 31, 1911. SeriaI No. 605,801.

The butylene glycol is represented in formula in the following manner:

CHr-CHOH I produce the butylene glycol in the following manner, whereby a highly concentrated solution of butylene glycol is directly obtained in one operation from acetaldehyde, 'and t he cost of evaporation, etc., is thereby very much diminished: I take ethyl alcohol (C H OH), which may be de-nat-ured without affecting the result. This ethyl alcohol is first oxidized. Preferably I accomplish this oxidation by the ordinary catalytic oxidation, such for instance, by using metallic platinum, copper or zinc The resultant is acetaldehyde (.C. ,H,O).. This acetaldehyde is then condensed. I have used for this condensation an aqueous solution of an alkaline carbonate, for instance, potassium carbonate; 450 grams of acetaldehyde were cooled to a low temperature say +5 to -10 C. preferably j5 C. and 200 grams or thereabout of powdered ice then added. A few drops of a cooled solution of potassium carbonate containing for example 19 grams of the carbonate in 80 cubic centimeters of Water were introduced into this mixture, the temperature not being allowed to rise above 10 C. and preferably not above 5 C. After standing some 10 or 15 minutes a further quantity of the carbonate solution was introduced to the mixture kept at a low temperature and again allowed to stand, contents, being kept as nearly as possible at a temperature of about 0C.

After the whole of the carbonate had been added, the reaction-product was kept in icev the formula of the glycerin trinitrate.

C. If the pure acetaldol is required this may be extracted with ether, but for the purpose of obtaining butylene glycol this is unneces- The condensation can be produced sarv. by other alkaline carbonate or a borate, phosphate, acetate or cyanid, of the metals of the alkalies or of the alkaline earths, and where, in the claims, I mention an alkaline salt, I mean to include as equivalents salts of metals of the alkalies or of the alkaline earths. The resultant of-this condensation is acetaldol (0 1E 0 This condensation product is then directly reduced to butylene glycol by means of a reducing agent, and I have employed the following method: The aqueous solution of acetaldoL obtained by condensing 450 grams of acetaldehyde with potassium corbonate was diluted to less than nine liters, say four liters, with water, the solution rendered neutral but preferably faintly acid by the addition of acid, say

hydrochloric acid, and then 200 grams or areduced pressure. Other amalgams may be used and, further, the aluminum or other met-a1 or an alloy or several metals may be used and also withoiutthe use of mercury. In this condition the butylene glycol exists in a concentrated aqueous =-s"olution and is isolated by simple. distillation, preferably under vacuum. This butylene glycol may then be nitrated in any known Way.

When I speak of glycerin trinitrate, of

, course I intend to include the glycerin monoand-di nitrates, although I have shown only In like manner, when I use the term butylene glycol dlnitrate I intend to include the butyproducing butylene glycol, which consists in condensing acetaldehyde to acetaldol in the presence of ice in contact with the acetaldehyde, adding an alkaline salt, gradually elevating the temperature during the condensing operation from substantially below 15 C. to not above substantially 15 0., diluting the acetaldol solution with less than about 15 parts of water and adding an acid to render the resultant liquid approximately neutral but preferably slightly acid, and then, without isolating the acetaldol, reducing the aqueous solution to butylene glycol by means of a metal amalgam.- 2. The hereinbefore described method of producing butylene glycol, which consists in condensing acetaldehyde to acetaldol in the presence of ice in contact with the acetaldehyde, adding potassium carbonate gradually in the form of a strong aqueous solution,

the condensing operation from substantially below 15 C. to not above substantially 15 (1., diluting the acetaldol solution with less than about 15 parts of water at a temperature not above substantially 15 C., adding an acid to render the resultant liquid approximately neutral but preferably slightly acid, and then, without isolating the acetaldol, reducing the aqueous solution to butylene glycol by means of aluminum amalgam.

In testimony of which invention, I have hereunto set my hand, at. Philadelphia, on this 23rd day of January, 1911.

' HAROLD HIBBERT.

Witnesses:

M. M. HAMILTON, A. J. MAGUIRE,

gradually elevating the temperature during v 

